Catalytic naphtha cracking catalyst and process

ABSTRACT

A process is disclosed for enhancing the production of light olefins using a catalyst with small pores. The catalyst comprises a layered zeolite material comprising an inner layer having pores of 8 or 10 membered rings and an outer layer having pores of 10 membered rings. The pores in the outer layer overlaying the pores in the inner layer. The zeolite has a silicon to aluminum atomic ratio of about 20 to about 200 and its surface acid sites external to the pores have been substantially neutralized.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a Division of application Ser. No. 10/246,801 filedSep. 17, 2002, now U.S. Pat. No. 6,867,341, the contents of which arehereby incorporated by reference in its entirety.

FIELD OF THE INVENTION

The present invention relates to a process for the production of lightolefins from a naphtha feed stream. This invention also relates to animproved zeolite used in the process for producing light olefins.

BACKGROUND OF THE INVENTION

Ethylene and propylene, light olefin hydrocarbons with two or threeatoms per molecule, respectively, are important chemicals for use in theproduction of other useful materials, such as polyethylene andpolypropylene. Polyethylene and polypropylene are two of the most commonplastics found in use today and have a wide variety of uses for both asa material fabrication and as a material for packaging. Other uses forethylene and propylene include the production of vinyl chloride,ethylene oxide, ethylbenzene and alcohol. Steam cracking or pyrolysis ofhydrocarbons produces essentially all of the ethylene and propylene.Hydrocarbons used as feedstock for light olefin production includenatural gas, petroleum liquids, and carbonaceous materials includingcoal, recycled plastics or any organic material.

An ethylene plant is a very complex combination of reaction and gasrecovery systems. The feedstock is charged to a cracking zone in thepresence of steam at effective thermal conditions to produce a pyrolysisreactor effluent gas mixture. The pyrolysis reactor effluent gas mixtureis stabilized and separated into purified components through a sequenceof cryogenic and conventional fractionation steps. A typical ethyleneseparation section of an ethylene plant containing both cryogenic andconventional fractionation steps to recover an ethylene product with apurity exceeding 99.5% ethylene is described in an article by V. Kaiserand M. Picciotti, entitled, “Better Ethylene Separation Unit.” Thearticle appeared in HYDROCARBON PROCESSING MAGAZINE, November 1988,pages 57-61 and is hereby incorporated by reference.

Methods are known for increasing the conversion of portions of theproducts of the ethylene production from a zeolitic cracking process toproduce more ethylene and propylene by a disproportionation ormetathesis of olefins. Such processes are disclosed in U.S. Pat. Nos.5,026,935 and 5,026,936 wherein a metathesis reaction step is employedin combination with a catalytic cracking step to produce more ethyleneand propylene by the metathesis of C₄ and heavier molecules. Thecatalytic cracking step employs a zeolitic catalyst to convert ahydrocarbon stream having 4 or more carbon atoms per molecule to produceolefins having fewer carbon atoms per molecule. The hydrocarbonfeedstream to the zeolitic catalyst typically contains a mixture of 40to 95 wt-% paraffins having 4 or more carbon atoms per molecule and 5 to60 wt-% olefins having 4 or more carbon atoms per molecule. In U.S. Pat.No. 5,043,522, it is disclosed that the preferred catalyst for such azeolitic cracking process is an acid zeolite, examples includes severalof the ZSM-type zeolites or the borosilicates. Of the ZSM-type zeolites,ZSM-5 was preferred. It was disclosed that other zeolites containingmaterials which could be used in the cracking process to produceethylene and propylene included zeolite A, zeolite X, zeolite Y, zeoliteZK-5, zeolite ZK-4, synthetic mordenite, dealuminized mordenite, as wellas naturally occurring zeolites including chabazite, faujasite,mordenite, and the like. Zeolites which were ion-exchanged to replacealkali metal present in the zeolite were preferred. Preferred cationexchange cations were hydrogen, ammonium, rare earth metals and mixturesthereof.

European Patent No. 109,059B1 discloses a process for the conversion ofa feedstream containing olefins having 4 to 12 carbon atoms per moleculeinto propylene by contacting the feedstream with a ZSM-5 or a ZSM-11zeolite having a silica to alumina atomic ratio less than or equal to300 at a temperature from 400 to 600° C. The ZSM-5 or ZSM-11 zeolite isexchanged with a hydrogen or an ammonium cation. The reference alsodiscloses that, although the conversion to propylene is enhanced by therecycle of any olefins with less than 4 carbon atoms per molecule,paraffins which do not react tend to build up in the recycle stream. Thereference provides an additional oligomerization step wherein theolefins having 4 carbon atoms are oligomerized to facilitate the removalof paraffins such as butane and particularly isobutane which aredifficult to separate from C₄ olefins by conventional fractionation. Ina related European Patent 109060B1, a process is disclosed for theconversion of butenes to propylene. The process comprises contactingbutenes with a zeolitic compound selected from the group consisting ofsilicalites, boralites, chromosilicates and those zeolites ZSM-5 andZSM-11 in which the mole ratio of silica to alumina is greater than orequal to 350. The conversion is carried out at a temperature from 500 to600° C. and at a space velocity of from 5 to 200 kg/hr of butenes per kgof pure zeolitic compound. The European Patent 109060B1 discloses theuse of silicalite-1 in an ion-exchanged, impregnated, or co-precipitatedform with a modifying element selected from the group consisting ofchromium, magnesium, calcium, strontium and barium.

Molecular sieves such as the microporous crystalline zeolite andnon-zeolitic catalysts, particularly silicoaluminophosphates (SAPO), areknown to promote the conversion of oxygenates to ethylene and propylenemixtures. Numerous patents describe this process for various types ofthese catalysts: U.S. Pat. Nos. 3,928,483, 4,025,575, 4,252,479 (Changet al.); U.S. Pat. No. 4,496,786 (Santilli et al.); U.S. Pat. No.4,547,616 (Avidan et al.); U.S. Pat. No. 4,677,243 (Kaiser); U.S. Pat.No. 4,843,183 (Inui); U.S. Pat. No. 4,499,314 (Seddon et al.); U.S. Pat.No. 4,447,669 (Harmon et al.); U.S. Pat. No. 5,095,163 (Barger); U.S.Pat. No. 5,191,141 (Barger); U.S. Pat. No. 5,126,308 (Barger); U.S. Pat.No. 4,973,792 (Lewis); and U.S. Pat. No. 4,861,938 (Lewis).

Generally, the heavier olefins having six or more carbon atoms permolecule which are produced in commercial ethylene plants are useful forthe production of aromatic hydrocarbons. Portions of the olefin productinclude olefins with four carbon atoms per molecule. This portionincludes both mono-olefins and di-olefins and some paraffins, includingbutane and iso-butane. Because the portion with four carbon atoms permolecule is generally less valuable and requires significant processingto separate di-olefins from the mono-olefins, processes are sought toimprove the utilization of this portion of the ethylene plant productand enhancing the overall yield of ethylene and propylene.

As the economy grows and expands, the demand for light olefins willincrease. Because of the limited availability and production of lightolefins from current methods, new methods are desired for increasingyields from existing sources of hydrocarbons.

BRIEF SUMMARY OF THE INVENTION

The present invention is a process for catalytic cracking of naphtha toethylene and propylene. In one embodiment, the process comprisescontacting a naphtha feedstock with a catalyst under reactionconditions. The catalyst comprises a molecular sieve havingsubstantially non-intersecting 10 membered ring channels with adimension in the range from about 0.1 micrometers to about 0.3micrometers in the channel direction. The 10 membered ring channels formelliptical pores with a pore index from about 22 Å² to about 30 Å². Thecatalyst further comprises a composition with a silicon to aluminumratio from about 20 to 200.

In another embodiment, the invention is a process for catalytic crackingof naphtha to ethylene and propylene. The process comprises contacting alayered catalyst with a naphtha feedstock. The layered catalyst is amolecular sieve with an inner structure having 8 or 10 membered rings,and an outer structure having 10 membered rings.

In another embodiment, the invention is a zeolite for selectivelyproducing ethylene and propylene. The zeolite is a crystal havingsubstantially non-intersecting channels where the crystal has adimension between 0.1 micrometers and 0.3 micrometers along thedirection of the channels. The channels are elliptically shaped poreswith a pore index from about 22 Å² to about 30 Å². The zeolite has asilicon to aluminum ratio from between 20 and 200 and is characterizedby hydrothermal stability up to about 700° C.

In another embodiment, the zeolite further comprises a material whereinthere is a gradient of aluminum in the pores. The aluminum has adecreasing concentration in the direction from the pore mouth to thepore interior.

Other objects, advantages and applications of the present invention willbecome apparent to those skilled in the art after a detailed descriptionof the invention.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a schematic diagram of an idealized pore in a zeolite crystalof the present invention;

FIG. 2 is a scanning electron micrograph of a ferrierite zeolite formedwith a pyridine template;

FIG. 3 is a scanning electron micrograph of a ferrierite zeolite formedwith a pyrrolidine template;

FIG. 4 is a scanning electron micrograph of a conventionally producedZSM-22 zeolite;

FIG. 5 is a scanning electron micrograph of a microcrystalline producedZSM-22 zeolite;

FIG. 6 is an NMR scan of a high ratio ferrierite zeolite before andafter subjecting the zeolite to severe steaming procedure;

FIG. 7 is a comparison plot for three zeolites of propylene selectivityvs. conversion;

FIG. 8 is a comparison plot for three zeolites of aromatics selectivityvs. conversion;

FIG. 9 is a comparison plot for three zeolites of ethylene selectivityvs. conversion; and

FIG. 10 is a plot showing the increased selectivity and conversion ofethylene and propylene.

DETAILED DESCRIPTION OF THE INVENTION

One embodiment of the invention is a process for selective catalyticcracking of naphtha to ethylene and propylene. The process comprisescontacting a naphtha feedstock with a catalyst and operating the processat reaction conditions.

A necessary feature of the process is the catalyst. The catalyst used isa molecular sieve having pores made of 10 membered rings and havingchannels with a length between about 0.1 micrometers to about 0.3micrometers. Additionally, the catalyst has a specifically distributedacid site density in the pores and can be characterized by a silicon toaluminum (Si:Al) atomic ratio from about 20 to about 200. This isequivalent to a silica to alumina (SiO₂:Al₂O₃) ratio from about 40 toabout 400. It is important to prevent reaction of ethylene and propyleneto side products, which requires a sufficiently low density of acidsites within the active region of the molecular sieve pores. By using amolecular sieve with a relatively high silica:alumina ratio the acidsites are sufficiently spaced.

Optimal catalytic cracking of naphtha to produce ethylene and propylenerequires zeolites having pores of sufficient size to admit moleculesfrom the naphtha feed while not too large to promote the formation ofaromatics or hydrogen transfer reactions with large transition states.Without being bound by any theory, it is believed that the pores have agenerally elliptical shape and have a pore index from about 22 Å² toabout 30 Å² allowing access of naphtha molecules into the pores. Thepore index as used herein is defined as the product of the two principaldiameters of a pore having an elliptically shaped cross-section. Theelliptical pores can also be circular wherein the pore index is equal tothe square of the diameter of a circular pore.

Examples of zeolites and their pore indexes are listed in Table 1, asfound in the Atlas of Zeolite Framework Types published by theInternational Zeolite Association. The Atlas of Zeolite Framework Typesis published on the Internet at (visited Aug. 22, 2002)<http://www.iza-structure.org/databases/> and is from Ch. Baerlocher, W.M. Meier and D. H. Olson, “Atlas of Zeolite Framework Types”, 5^(th) ed.Elsevier, Amsterdam, 2001.

TABLE 1 Pore Pore Zeolite Structure Dimensions Index ITQ-3 ITE 3.8 Å by4.3 Å 16.3 Å² ZK-4 LTA 4.1 Å by 4.1 Å 16.8 Å² SSZ-23 STT 3.7 Å by 5.3 Å19.6 Å² EU-1 EUO 4.1 Å by 5.4 Å 22.1 Å² MCM-22 MWW 4.0 Å by 5.5 Å   22Å² Ferrierite FER 4.2 Å by 5.4 Å 22.7 Å² ZSM-23 MTT 4.5 Å by 5.2 Å 23.4Å² ZSM-22 TON 4.6 Å by 5.7 Å 26.2 Å²

A preferred zeolite is a ferrierite. Ferrierite is a two-dimensionalchannel zeolite structure with 8 and 10 member ring channels. The 10member channels have an approximately ellipsoid cross section with twodiameters defining the ellipsoid of 5.4 Å and 4.2 Å. The ferrierite 10member rings have substantially non-intersecting channels.

The synthesis of zeolites of the present invention can be formed byhydrothermal crystallization from a reaction mixture containing thedesired amounts of silica and alumina and a templating agent. Zeoliticsynthesis processes are known in the art, and can be found in U.S. Pat.Nos. 4,554,143; 4,440,871; 4,853,197; 4,793,984; 4,752,651 and4,310,440, all of which are incorporated by reference.

An advantage of this process with these zeolites is control over thepropylene to ethylene ratio. This process produces a higher ratio ofpropylene to ethylene and can achieve a ratio of greater than 0.9.Another advantage to the present invention is operation of the processat lower temperatures. The process is operated at about 150° C. to 200°C. lower than conventional steam cracking processes of temperaturesaround 850° C. This can result in considerable energy savings duringoperation. There will also be a saving in the cost of equipment of thereactor because of simplification of the metallurgical requirements.

In a second embodiment, the invention is a process for selectivecatalytic cracking of naphtha to ethylene and propylene. The processcomprises contacting a naphtha feedstock with a catalyst and operatingthe process at reaction conditions. The catalyst uses a molecular sievemade of a layered material comprising at least two layers of zeolite.The layered zeolite includes at least two layers wherein there is atleast one inner zeolite layer and at least one outer zeolite layer. Theinner zeolite layer has a first structure and includes pores made of 8membered rings, 10 membered rings, or a mixture of 8 and 10 memberedrings. The outer zeolite layer has a second structure and includes poresmade of 10 membered rings, wherein the pores of the outer layer overlaythe pores of the inner layer.

The inner layer is a zeolite with pores small enough to suppress theformation of aromatics. Examples of such zeolites include, but are notlimited to, wenkite, chabazite, dachiardite, erionite, zeolite A, ZK-4,epistilbite, laumontite, wienebeneite, EU-1, UZM-5, UZM-9 and UZM-12.Combinations of zeolites can also be used to form an interior layer, ora plurality of interior layers with one or more of the structureslisted. The outer layer is a zeolite with pores large enough to admitthe diffusion of naphthenes and isoparaffins that are present incrackable hydrocarbon feedstocks. Examples of such zeolites include, butare not limited to, ferrierite, ZSM-22, ZSM-23, ZSM-50, ZSM-57, ZSM-11,ZSM-5, NU-87 and clinoptilolite. Combinations of zeolites can also beused to form an outer layer, or a plurality of outer layers with one ormore of the structures listed.

The resulting layered catalyst is an improved catalyst relative to eachof the individual catalysts used for synthesizing the layered catalyst.The improved catalyst will yield higher amounts of ethylene andpropylene from a hydrocarbon feedstock because the larger outer poresallow larger hydrocarbon molecules to get in and to get activated. Asthe molecules diffuse into the smaller pores, the smaller pores restrictthe amount of aromatic formation favoring the conversion to lightolefins because of the restrictive pore size in the inner layers.

The inner layer, or layers, has a dimension from about 0.1 micrometersto about 5 micrometers, with a preferred dimension of 0.1 micrometers to0.5 micrometers. This dimension is the thickness of the layers if thelayers are grown over an inert core, or the effective diameter of acatalyst particle grown. By effective diameter is meant, fornon-spherical shapes, the diameter that the shaped particle would haveif it were molded into a sphere. In a preferred embodiment, the driedshaped particles are substantially spherical in shape.

The outer layer, or layers, has a dimension from about 0.1 micrometersto about 1 micrometer, with a preferred dimension from 0.1 micrometersto 0.2 micrometers. The overall dimension of the catalyst particles ispreferably in the range of 0.1 micrometers to 5 micrometers with a morepreferred range of 0.5 micrometers to 2 micrometers.

In an alternate embodiment, the layered zeolite has an inert inner core.This embodiment comprises an inert inner core and at least one layer ofan aluminum containing zeolite on top of the inert core. An inert coreas used herein is any material that is unreactive for the presentapplication, and includes cores made of a material that is notaccessible to the hydrocarbons with respect to the materials acidity.The inaccessibility can be due to the lack of pores, pores that are tosmall to admit the hydrocarbons, or a core that has a layer of an inertand impermeable material between the inner core and the zeolite. Thisallows for the zeolite to be increased in size while maintaining a highsurface to volume ratio of the active catalyst region. This embodimentalso provides for short active regions accessible to naphtha moleculesand limiting the residence times of naphtha molecules in catalyticallyactive regions. This embodiment provides larger crystals that areequivalent to smaller or very thin crystals of zeolite as regards thecatalytic performance, such as when the use of larger crystals isnecessary and smaller crystals are not practical for hydrocarboncracking processes. This embodiment, as it can provide a thin reactionzone, can produce higher yields of ethylene and propylene while limitingthe amount of ethylene and propylene further reacting to other undesiredproducts. This embodiment also helps to overcome problems associatedwith limitations associated with intraparticle diffusion.

An optional aspect of the process is using a zeolite with an aluminumconcentration decreasing as one moves down a pore from the mouth of thepore to the interior of the pore. FIG. 1 represents a diagram of a porefor an idealized zeolite crystal of the present invention. The zeolitecrystal 10 is made up of a series of substantially non-intersectingpores 12. A pore 12 has a pore mouth 16 defined by the edge 14 of thepore 12. The zeolite crystal 10 as used with the present invention has arelatively high aluminum concentration region 18 near the pore mouth 16with a decreasing aluminum concentration as one moves down the pore 12away from the pore mouth 16. The crystal 10 has an interior pore region20 which has a relatively low aluminum concentration. The relativelyhigh and low aluminum concentrations are relative to the overall averagealuminum concentration in the zeolite pores 12 framework. A preferredembodiment of the zeolite is for a distribution of aluminumconcentration within the pore 12. The preferred distribution is agradient with a relatively high alumina concentration near the poremouth and a lower concentration in the pore interior. The preferredgradient is for the relatively high aluminum concentration to be atleast 1.5 times as great as the average aluminum concentration in thepores 12.

Another optional aspect of this process is using a zeolite wherein thecrystal 10, as shown in FIG. 1, has an exterior surface 22, and theexterior surface 22 has acid sites that are neutralized. This producesan exterior surface 22 that is unreactive when exposed to the naphtha.This presents a zeolite crystal with a sharp increase in aluminumconcentration as one traverses from an external surface to just inside apore, and the aluminum concentration then decreases as one travels downthe pore. By neutralizing the acid sites on the external surface, thereaction for cracking a naphtha molecule is prevented on the surfaceoutside of the pores. This prevents the olefinic molecules generated inthe pores of the zeolite from further reacting to produce undesirableproducts. This also limits the production of larger olefins andaromatics that might be produced on external surfaces of the zeolite.The exterior surface 22 may be neutralized in a number of ways. Onemethod of neutralizing the zeolite surface 22 is to coat the surfacewith a non-reactive material, such as continuing growing the crystalwith an aluminum free inert material. It is preferred to have a verythin layer of only a few molecules thickness. An alternate to coveringthe entire zeolite surface 22 is to use a chemical, such as silane, thatwill cover the surface aluminum. An alternative method of neutralizingthe surface is to remove the aluminum on the surface 22 of the zeolite.Removal of the aluminum can be accomplished by treating the zeolite withan appropriate chemical such as EDTA (ethylenediamine tetraacetic acid)or AFS (ammonium hexafluorosilicate).

The naphtha components react with acid sites within the pores and createlight hydrocarbons, specifically ethylene and propylene. The acid siteswithin the pores are sufficiently spaced and have decreasingconcentration when one travels from the pore mouth to the interior ofthe pore. The spacing and decreasing concentration of acid sitesinhibits the continuation of reaction to prevent the formation ofundesirable products, such as aromatics or subsequent reacting of theethylene or propylene produced. The spacing and decreasing concentrationas well as the pore size and shape of the pores also prevents theformation of aromatics. By using a zeolite with a relatively small poresize also prevents the formation of aromatics in the pores.

An embodiment of this invention is a zeolite structure with uniquealuminum distribution and crystal dimensions. A zeolite comprising acrystal having substantially non-intersecting channels is grown. Thechannels are made of 10 membered rings and the crystal size is limitedto less than 0.5 micrometers in the direction of the 10 membered ringchannels. A preferred crystal dimension is in the range from about 0.1micrometers to about 0.3 micrometers.

An aspect of the invention is the residence time of the hydrocarbon tobe reacted in the catalyst pores. Using a catalyst with a relativelyshort channel length of less than 0.3 micrometers limits the residencetime of the hydrocarbon in the pores. The desired morphology of thecatalyst is for a relatively short channel length of the pores. Thepreferred pore channel length is from about 0.1 micrometers to about 0.3micrometers. The morphology limits the residence time of hydrocarbonswithin the pore channels. The morphology can be studied with electronmicroscopy. FIGS. 2 and 3 show scanning electron micrographs (SEM) offerrierite with two different templates. FIG. 2 shows a pyridinetemplate which produces a conventional platy morphology of theferrierite. The pyridine templated ferrierite has a silica to aluminaratio of 61.7. FIG. 3 shows a pyrrolidine template of ferrieriteproducing small crystals. The pyrrolidine templated ferrierite has asilica to alumina ratio of 64.4. From transmission electron microscopy(TEM) the 10 and 8 membered-ring channels of the platy morphologyferrierite are parallel to the plates and consequently are too long. Theplates have a thickness of 0.1 to 0.2 micrometers and there are nochannels in that direction. Using the pyrrolidine templated ferrierite,smaller crystals are produced with channel lengths in the preferredrange. Another zeolite, ZSM-22, is shown in FIGS. 4 and 5. When ZSM-22is conventionally produced as shown in FIG. 4, a needle like structureis created and the structure has pore channels parallel to thestructure's principal axis. The channels are consequently too long. Byselection of an alternate template, a microcrystalline ZSM-22 isproduced, as shown in FIG. 5. The microcrystalline ZSM-22 has channellengths in the desired range from about 0.1 to about 0.3 micrometers.

A preferred zeolite can be found in a modified ferrierite. Inferrierite, the only channels available for bulky reactant molecules inthe feed are the 10 membered ring channels. Smaller 8 membered ringchannels do not allow access to bulky reactant molecules such asisoalkanes and naphthenes, but do provide access for movement of smallproduct molecules such as ethylene and propylene. The 10 membered ringchannels form elliptically shaped pores wherein the elliptical poreshave a pore index from about 22 Å² to about 30 Å². The zeolite ischaracterized by a silica: alumina ratio from about 40 to about 400, andfurther characterized in that the zeolite crystal is hydrothermallystable to about 690° C. The hydrothermal stability is important as theprocess is carried out at a temperature from about 550° C. to about 700°C., with a preferred range from about 600° C. to about 675° C. Theprocess also includes carrying out catalyst regeneration at atemperature of about 15° C. to 25° C. higher that the inlet reactiontemperature. A ferrierite zeolite with the desired properties was testedunder severe steaming conditions. Nuclear magnetic resonance (NMR) ofthe zeolite before and after the severe steaming procedure indicated aneffective amount of the framework alumina remained intact, as shown inFIG. 6.

Pore diameter can be controlled by the introduction of non-frameworkspecies, for example, by cation exchange. Examples of species for use incation exchange include, but are not limited to, transition metals,non-framework aluminum, potassium, sodium, magnesium, calcium,strontuim, phosphorus, and mixtures thereof.

An alternate embodiment of a zeolite of the present invention is alayered zeolite. The layered zeolite is characterized by an innerstructure having pores small enough to suppress aromatic formation fromethylene and propylene, and an outer layer having larger pores foradmitting naphthenes and iso-paraffins. The inner layers have pores madefrom a zeolitic material having large 8 membered rings or small 10membered rings. A thin outer layer is then grown epitaxially over theinner layer, where the outer layer has larger 10 membered rings.

Without being bound to a particular theory, it is believed that controlof the Al content and its uniform distribution over the potential sitesis important to maximizing the activity, selectivity, and stability ofmolecular sieve for use in the production of light olefins from naphtha.

Preferably, the zeolites include the following additional constraints.During reaction with hydrocarbon feed, channels can be partially ortotally blocked as a result of deposition of coke molecules. Blockagecan also result from deposition of other molecules such as non-frameworkaluminum. Partial or complete blockage of a channel will make a portionor all of the channel ineffective for continuing cracking reactions. Itis important, therefore, that the channels have a small dimension, whileat the same time the catalyst particles must be above a minimum size soas not to be carried out of the reactor with a stream of products.

One method of making these zeolites includes initially growing crystalswith an aluminum free material to provide inert inner cores. The inertcores are used as seeds over which an aluminum containing zeolite isgrown epitaxially until an outer layer having a desired thickness isachieved. A desired outer layer thickness is in the range from about 0.1micrometers to about 0.5 micrometers. The outer surface external to thepores is further processed to neutralize the aluminum on the outersurface. One manner of neutralizing this outer surface is to furthergrow epitaxially a thin layer of aluminum free material.

The process of the invention comprises contacting a naphtha feedstream,in gaseous form, with any of the above described catalysts. Thecontacting of the naphtha with the catalyst occurs, for example, in afluidized catalytic cracking (FCC) type reactor. The process entailsfeeding the hot catalyst and the vaporized, preheated naphtha into areactor vessel, wherein the catalyst mixes with the gas and is entrainedwith the gas, and the gas-catalyst mixture reacts under operatingconditions producing a product gas and used catalyst. The product gasand used catalyst exit the reactor where the used catalyst isdisentrained from the product gas, leaving a product gas stream and acatalyst stream. Some of the catalyst is then sent to a regeneratorwhere carbon deposits are substantially removed. The choice of reactorcan be any fluidized type of reactor for intimately mixing the naphthafeedstream with the catalyst. Reactors of this type are well known tothose skilled in the art. A fluidized reactor usable in this inventionis described in U.S. Pat. No. 6,183,699, which is incorporated byreference.

Alternate feedstocks that are crackable to ethylene and propyleneinclude gas oil, vacuum gas oil, and Fischer-Tropsch wax. Preferably,the feedstock has been processed to remove aromatics. An optionalconfiguration in the present invention includes a hydrocarbon separationunit, for processing the product gas stream. The product gas stream isseparated into an ethylene product stream, a propylene product stream,and a plurality of recycle streams. The recycle streams are optionallyfurther separated into an ethane stream, a propane stream, a butane andbutene stream, and a non-aromatic naphtha liquids stream. The recyclestreams are directed back to the reactor and are optionally, directedinto the reactor at a single location, at different locations, or evendirected to different reactors arrayed in a parallel configuration.

The aspect of using different reactors in a parallel configurationallows for varying control over the temperatures and pressures for thedifferent individual reactors. The different reactors allows fordifferent temperatures of the individual reactors, different operatingpressures, and different residence times. The use of different reactors,optionally, allows for the use of different modified catalysts for usewith different feedstocks. In the option of using different catalysts,different catalyst regeneration units are also used for regeneratingindividual types of catalysts directed to the different reactors.

One aspect of the process operating conditions is the temperature atwhich the reaction is carried out. The reactions can be carried outbetween a temperature of about 550° C. to about 700° C. A preferredtemperature for operating the process is to be in the range from about600° C. to about 675° C. with a more preferred operating temperature ofabout 650° C. to about 670° C.

Another aspect of the process is operating the reaction at an elevatedpressure. A preferred operating pressure is in the range from about 101kPa (0 psig) to about 3550 kPa (500 psig). A more preferred operatingpressure is from about 135 kPa (5 psig) to about 450 kPa (50 psig).

Another aspect of the process is the optional further addition of asteam diluent, wherein the steam diluent is injected into the mixture ata rate of up to five times the hydrocarbon ratio on a volume, or mole,basis in the gas phase. The performance can be enhanced by lowering thepartial pressure of the hydrocarbons. Adding a diluent, such as steam oran inert gas, lowers the partial pressure while maintaining theoperating temperature and pressure of the system.

When the process is carried out in a batch process, the contact timevaries from about 0.1 seconds to about 5 hours and preferably from about0.1 seconds to about 0.1 hour. The longer contact times are used atlower temperatures while shorter times are used at higher temperatures,assuming all other process variables are equal. Further, when theprocess is carried out in a continuous mode, the weight hourly spacevelocity (WHSV) based on the total feed (including any diluents) canvary from about 5 hr⁻¹ to about 200 hr⁻¹ and preferably from about 10hr⁻¹ to about 100 hr⁻¹. As is understood in the art, the weight hourlyspace velocity is the weight flow of the feed divided by the catalystweight.

Results from runs with the modified zeolites demonstrate the increasedconversion. Of note is the increased ratio of propylene to ethyleneproduced in the conversions. The results of naphtha cracking usingseveral modified zeolites of the present invention are shown in Table 2.The results are for a single pass of naphtha with zeolites in amicroactivity test unit. The naphtha is a full boiling naphtha in the C₅to C₁₁ range containing about 87% paraffins and naphthenes and about 13%aromatics. The reaction conditions were an inlet temperature of 665° C.,reactor pressure of about 150 kPa (7 psig), and a WHSV of about 19during injection. All of the zeolites were comprised of 80% zeolite and20% binder. Of note, are the ratios of propylene to ethylene in thetests. The ratio of propylene to ethylene ranged from 0.76 to 1.18. Thisexhibits the desired ability to increase the propylene yield during theproduction of ethylene and propylene. In addition, recycling the C₂ andheavier hydrocarbons will increase the yield of ethylene and propylenefrom the naphtha feedstock.

TABLE 2a Beta 1 Beta 2 Omega Mordenite Pore Size 6.4 × 7.6 6.4 × 7.6 7.4× 7.4 6.5 × 7   Pore Size Index 48.6 48.6 54.8 45.5 Si/Al₂ 24 24 7 20Ring size 12 12 12 12 Yields, wt. % H2 3 5 3 3 C₁-C₂ 12 20 13 17 C₂═ 1 27 2 C₃═ 0 1 4 1 C₃-C₄ 1 1 19 2 C₅+ 46 26 33 41 Coke 37 45 21 34

TABLE 2b EU-1 Ferrierite ZSM-22 ZSM-23 Pore Size 4.1 × 5.4 4.2 × 5.4 4.4× 5.5 4.5 × 5.2 Pore Size Index 22.1 22.7 24.2 23.4 Si/Al₂ 26 76 60 50Ring size 10 10 10 10 Yields, wt. % H2 1 1 1 1 C₁-C₂ 9 9 12 12 C₂═ 16 1717 17 C₃═ 13 18 15 16 C₃-C₄ 14 12 10 11 C₅+ 43 40 40 39 Coke 4 3 5 4

Tables 2a and 2b show the yields of several templated zeolites havingthe desired properties and several zeolites having undesired properties.The main feature screened shows that zeolites having high pore sizeindices, or ring sizes larger than 10 membered rings, have a lowselectivity for ethylene and propylene, and therefore are unsuitable forthis process.

TABLE 3 Catalyst Designation Ferrierite ZSM-23 ZSM-22 SUZ-4 EU-1 Gmzeolite/ 0.148 0.152 0.152 0.152 0.152 gm naphtha Yields, wt % H₂ 0.60.9 0.9 0.7 0.6 C₁ 4.8 5.6 6.2 4.0 4.2 C₂═ 17.1 17.3 17.1 12.7 15.7 C₂4.2 4.8 5.3 2.5 4.9 C₃═ 17.6 16.2 15.1 15.0 13.1 C₃ 3.2 3.8 3.5 3.3 5.5C₄═ 6.4 5.4 1.4 6.5 6.4 C₄ 2.5 2.0 5.2 3.5 1.6 C₅+ Gas 30.0 33.8 34.036.6 34.8 Liquid 10.3 6.2 6.2 10.2 9.0 Coke 3.3 4.0 5.1 5.0 4.2 C₃═/C₂═1.03 0.88 0.88 1.17 0.83 C₂═ + C₃═, 34.7 32.3 32.2 27.4 28.8 %

Table 3 shows molecular sieves when prepared to produce the desiredproperties relative to pore size, pore channel length, and acid sitedensity provides good selectivity and conversion of naphtha to propyleneand ethylene. This is further illustrated in FIGS. 7 to 10, comparingferrierite with a zeolite lacking the desired characteristics, i.e. anMFI type zeolite. FIGS. 7 to 10 are for the results of pulsemicro-reactor tests of naphtha cracking over high and low ratioferrierites and MFI zeolites, showing percent selectivity vs. percentconversion. The high and low ratio refer to the Si:Al atomic ratios. Thereaction conditions of the micro-reactor tests are 5000 GHSV (gas hourlyspace velocity) and a temperature of 650° C. In FIG. 7, the ferrierite,having desired characteristics and prepared with a template, produces ahigh propylene selectivity and high conversion. FIG. 8 shows the desiredferrierite has a low aromatics selectivity and high conversion whencompared with a zeolite having an MFI framework structure and aferrierite not having desired characteristics (low ratio ferrierite).FIG. 9 shows a comparison of the desired ferrierite with a low ratioferrierite and a zeolite with an MFI framework structure for ethyleneproduction. The ethylene selectivity for the ferrierites is greater thanthe MFI zeolite for which the pore size index is much higher. Thetemplated ferrierite also has an improved conversion over the low ratioferrierite. The overall improvement is best seen when comparing thetotal ethylene and propylene selectivity as shown in FIG. 10. The highratio ferrierite demonstrates significant improvement in selectivity andconversion over a low ratio ferrierite and an MFI zeolite. The MFIzeolite has a 3-d interconnected pore structure and allows for greaterconversion of naphtha to aromatics, an undesired product that needs tobe separated from any product stream as well as any recycle stream. Thedisadvantage of the low ratio ferrierite is the high acid site densitywhich causes Al to come out of the framework under simple reactionconditions. The templated ferrierite was made with a lower acid sitedensity than the low ratio ferrierite. By increasing the silica toalumina ratio there is an improvement in propylene selectivity andnaphtha conversion, while maintaining a low aromatics generation.

TABLE 4 Cat. Low ratio High ratio ZSM-35 Designation Fer Fer Fer Si/Al₂17 74 20.1 Crystallite size, 1-2 1-2 0.2 micrometers Conversion 52 79 82Selectivities H2 1 1 2 C₁ 10 7 14 C₂═ 26 25 25 C₂ 7 6 10 C₃═ 28 26 21 C₃3 5 3 C₄═ 10 9 7 C₄ 3 4 4 Aromatics 4 13 1 Coke 8 4 13

Table 4 further lists a comparison of two aspects of the inventionshowing a comparison of the results of tests using a low ratioferrierite, a high ratio ferrierite and a ferrierite with a smallcrystalline size. The tests were run in a microreactor with an inletfeed temperature of 665° C., other operating conditions were asdescribed above. A comparison of the low ratio ferrierite with the highratio ferrierite shows significant improvement in the conversion of thenaphtha feed. In addition, a comparison of the low ratio ferrierite withrelatively large crystallite size of 1-2 micrometers, with a low ratioferrierite having a small crystallite size of 0.2 micrometersdemonstrates significant improvement in the conversion of the naphthafeed with decrease in crystal size. These are further demonstrations ofthe importance of the silicon to aluminum atomic ratio and the controlof the size of channels within the crystal through the sizing of thecatalyst crystals.

Without being bound by any theory, it is believed that the improvementin ethylene and propylene production results from the combinedcharacteristics of the molecular sieves defined in this invention. Thepore must be of sufficient size to permit entry by larger hydrocarbons,particularly isoparaffins and naphthenes. At the same time the poresmust be sufficiently small to inhibit the production of aromaticcompounds within the pores but not limit the cracking to lower molecularweight olefins. The acid sites need sufficient spacing, or low enoughalumina density, to limit undesirable reactions of ethylene andpropylene, and to minimize the removal of Al from the framework undercalcination, reaction and regeneration conditions. The residence timewithin the pores is an additional factor controlling the production ofethylene and propylene, and one which is controlled by limiting thelength of the pore channels.

While the invention has been described with what are presentlyconsidered the preferred embodiments, it is to be understood that theinvention is not limited to the disclosed embodiments, but is intendedto cover various modifications and equivalent arrangements included withthe scope of the appended claims.

1. A layered zeolite material comprising: an inner layer having poresmade of 8 or 10 membered rings having a first structure; and an outerlayer having pores made of 10 membered rings having a second structure,wherein the pores in the second structure overlay the pores in the firststructure; wherein the zeolite has a silicon to aluminum atomic ratiofrom about 20 to about 200, and surface acid sites external to the poreshave been substantially neutralized.
 2. The zeolite of claim 1 whereinthe inner layer comprises a zeolite selected from the group consistingof wenkite, chabazite, dachiardite, erionite, zeolite A, ZK-4,epistilbite, laumontite, weinebeneite, EU-1, and mixtures thereof. 3.The zeolite of claim 1 wherein the outer layer comprises a zeoliteselected from the group consisting of ferrierite, ZSM-22, ZSM-23,ZSM-50, ZSM-57, ZSM-11, ZSM-5, SUZ-4, NIJ-87clinoptilolite, and mixturesthereof.
 4. The zeolite of claim 1 wherein the inner layer has athickness between about 0.1 micrometers and about 5 micrometers.
 5. Thezeolite of claim 4 wherein the inner layer has a thickness between about0.1 micrometers and about 0.5 micrometers.
 6. The zeolite of claim 1wherein the outer layer has a thickness between about 0.1 micrometersand about 1 micrometers.
 7. The zeolite of claim 6 wherein the outerlayer has a thickness between about 0.1 micrometers and about 0.2micrometers.